JPH022327A - Sweetener having heterocyclic group - Google Patents

Abstract

PURPOSE: To provide a sweetener represented by a specified structural formula, having sweetness similar to that of sucrose, readily soluble in water, soluble in a carbonated drink of a proper pH, etc., and useful for a sweet food such as a soft drink. CONSTITUTION: This sweetener is represented by structural formula I, wherein R is a monocyclic heterocyclic group represented by formula II (where X is Cl, CN, etc.), etc., or a bicyclic heterocyclic group represented by formula III (where G1 is CH, etc., G2 is CH2 , CO, etc., and each of G3 and G4 is CH, CCH3 , etc.), etc., R is preferably 2-cyanopyridon-5-yl or 2-cyanopyrimidin-5-yl, A is O, S, NH, etc., (n) is 1-2 and B is COOH, etc.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention is particularly applicable to sweet foods, beverages, sugar confectionery, bread confectionery,
The present invention relates to sweeteners with heterocyclic groups useful for use in chewing gums, hygiene products, cosmetics, cosmetic supplies, pharmaceutical and veterinary products, etc., and to preparations and compositions containing such sweeteners.

``Prior art'' Among the chemical compounds that exhibit sweetness properties, ``Suosan'' (5g
osan) J and its derivatives constitute a chemical series that has been extensively studied since its discovery by Peterson and Mueller in 1948.

For example, Mr. Beet, “Structure and activity relationships in human chemosensation,” Applied Science 1978, 336.
"Advances in Sweeteners" published by London, Crospi and Wingard, pp. 337, Applied Science, 1979, pp. 160, published by London, Cinch, Nofre and Beitabi, 2. Lebeasm, Ulers, Forsch,
See 1982, Vol. 175, pp. 266-268. However, some of these compounds contain highly toxic molecules, in this case 4
- Not used commercially because it liberates nitroaniline. Moreover, these compounds are only slightly soluble in acidic p)l solutions of (pH 2.5-3), the conditions of use that normally sweeten carbonated beverages (soft drinks), which therefore constitute the main market for sweeteners. There wasn't.

US Patent Application No. 836,071 discloses sweeteners of the following general formula.

However, A can be N, N+ or C, and N+ can be ca-i: Therefore, m is l when A is N, 2 when A is N'''' or C, and n is , l or 2, B is CN, H, No, , OCH, or 5O2R when n is 1, and R is alkyl having up to 10 carbon atoms,
is a cycloalkyl or allyl group, when n is 2, it is CN, H or OCH, and when B is CN, H or OCH3, X is CN or NO
□, and when B is No or 5o2R, CIl, CN.

COCHs, F, H or No, M is H, Nl
, K, NH4, l/2Ca or l/2Mg groups have been proposed.

[Problem to be Solved by the Invention] Suosan and Derivatives and U.S. Patent Application No. 836.07
In particular, the sweetener described in No. 1 dissolved too little at a pH of 2.5 to 3, which is present in soft drinks such as carbonated drinks, which constitute the main market for synthetic sweeteners.

[Means for Solving the Problems] The improved sweetener according to the present invention aims to eliminate these drawbacks.

The sweetener of the present invention has the following general formula, where R is
a heterocyclic group that is monocyclic or bicyclic, the monocyclic group being selected from the following group, provided that X is C
M, CN or NO2 group, the bicyclic group is selected from the following group, R-NHC-NH-(CH2), -B provided that G is CH or N, G2 is CH2 ,C01NH,NCH,,0 female is S, G and G are CH, CCH,, N or No, the A is 0, S, NH or N-CN, NH is hydrochloric acid It is characterized in that it is chlorinated in a salt form, the n is 1 or 2, and the B is COOH or a sodium, potassium, ammonium, calcium or magnesium salt.

In other words, the sweeteners of the present invention are derived from Suosan or its derivatives and the sweeteners described in U.S. Patent Application No. 836,071 by replacing a carbocyclic group (XCiH4) with a heterocyclic group, i.e., a heterocyclic group (R). The difference is that it has been replaced with
2,5-3) has the effect of increasing solubility in acid conditions.

Furthermore, substituting a carbocyclic group (X-C, H,) with a heterocyclic group (R) slightly improves the sweetness of the sweetener, but it does not change the molecular structure of the sweetener. Even a single violet modification was totally unexpected given the common sense that it would suppress sweetness properties where the relationship between structure and sweetness activity is poorly predictable. M.G.

J. Beetz, Structure-Activity Relationships in Human Chemosensation, Applied Science, Published London 1978, 259-3.
See page 62.

Advantageously, in the sweetness according to the invention R is a 2-cyanopyrid-5-yl group or a 2-cyanopyrimidine-5
-nyl group, the above A is 0 or NH, and the above n is 1 when A is NH, or 2 when A is O.

Of course, the present invention can also be used to prepare sweet foods, beverages, candies, pastries, chewing gums, sanitary products, cosmetics, toiletries, pharmaceutical and veterinary preparations by adding appropriate amounts of one or more sweetness levels according to the invention. Regarding the method of forming etc. A suitable or "effective amount" refers to an amount of sweetener sufficient to produce a sweet sensation.

The invention, of course, relates to preparations sweetened by the method according to the invention.

The present invention, of course, relates to sweetening compositions comprising an effective amount of at least one sweetening agent according to the invention and a suitable carrier or bulking agent.

The invention, of course, relates to a sweetening composition characterized in that it consists of an effective amount of one or more sweetening agents according to the invention and one or more other sweetening agents.

Products sweetened by the sweeteners of the present invention include all products in which a sweetening ingredient is desired, in particular foods for human or animal consumption, alcoholic beverages, non-alcoholic beverages, juices, beverages such as carbonated drinks, sugar confectionery. , bakery products, chewing gum, hygiene products, cosmetics, pharmaceutical and veterinary preparations and their equivalents.

The sweetener of the present invention has a purity of 100% and can be added to cosmetics etc. to add sweetness. However, due to its high sweetness properties, the sweetener of the present invention can be used in combination with an optimal carrier or filler. The carrier or filler may be polydextrose, starch, maltodextrin, cellulose, methylcellulose, carboxymethylcellulose, hydroquine methylcellulose, fine cellulose, sorta alginate, hectin, gum, lactose, maltose, crucose, leucine, glycerol, mannitol. ,
Sorbitol, sodium bicarbonate, phosphoric acid, citric acid,
It is preferably selected from the group consisting of tartaric acid, thumaric acid, benzoic acid, sorbic acid or propionic acid and their sodium, potassium and calcium salts and their respective proportions.

The sweetener of the present invention can be used as a single sweetener or as a mixture of two or more sweeteners of the present invention in beauty or cosmetic products. The sweetener of the present invention includes sugar (sucrose), corn syrup, 7-lactose, Semi depeptide derivatives (aspartame, alitame), dihydrochalcone, dehydrated isomaltose, stevioside, L-sugar, glycyrrhizine, kylitol, Sorbitol, mannitol, acesulfuric acid - such as sacchulin and their sodium, potassium, ammonium and calcium salts, cyclamenic acid and their sodium, potassium, ammonium and calcium salts, trichlorogalactosacrose, monellin, thaumatin and equivalents. Can be used in combination with other sweeteners.

The method of preparing the sweetener of the present invention varies depending on whether A is 0, S, NH or NCN in the general formula of the desired sweetener.

The preparation method comprises the following condensation reaction.

(1) RNH2 and A = C = N-(CHz)
, -BA is O, the reaction is carried out in an organic solvent such as acetotrile or chloroform at room temperature or boiling temperature.

(2) R-N=C=A and H2N-(CH2)--C00H When A is 0 or S, the reaction is carried out in water at room temperature,
R-N=C=A dissolves in organic solvents such as benzene or chlorobenzene.

(3) R-NH-C3-NH2 and H! N-(C
Hz)--B.

When A is NH, or RNHC3-NH(CH2)-B and NH, or RNHC9NH(CHz), B and H2N CN When A is NCN, the reaction is carried out in the presence of a condensing agent such as dicyclohexylcarbodiimide. Effective at room temperature or boiling temperature.

(4) R-NH=CCIl-NH-(CH,), -B and NH.

When A or NH, R-NH-CCII-NH(CH2
), -B is obtained by condensation of RN=CCQ2 and H2N -(CH2), B in chloroform or ethyl acetate at room temperature, and the reaction mixture is NH.

was heated to 70°C for condensation with

(5) R-NH-C(=A)-5CH, and H2N
-(CH2), -COOH When A is NH or NCN, the reaction is NaOH or NCN.
It was carried out in an ethanol/water mixture at boiling temperature in the presence of a base such as (C:Hs)i.

(6) R=NH-C(-NCN)-NH-(CH,).

B and aqueous hydrochloric acid solution When A was NH, hydrolysis was carried out at 70°C.

In the general formula of the drug used, R and n apply the above definitions, B corresponds to a protected carboxyl group, for example in the form of an ester such as methyl, ethyl, tertiary butyl, benzyl ester, etc. is removed by suitable means such as oxidation with NaOH or hydrolysis with hydrochloric acid.

In order to obtain the compounds of the present invention, the first to sixth methods are carried out using the experimental conditions and values of n and A, R and B specified for each method.
can be selected by a person skilled in the art as a characteristic function of .

The compositions of the invention can exist in acid or alkali (salt) form. These compounds can therefore be converted to alkalis by physiologically acceptable inorganic or organic bases, or to physiologically acceptable inorganic or organic acids when A is NH. One of the various methods of preparing these salts consists of concentrating an aqueous mixture of the compounds of the invention and the alcoholic salts or organic acids to dryness under vacuum.

Preferred salts of the invention are sodium, ammonium, carunium and magnenium salts, or chloride when A is NH.

Purification of the compounds of the invention can be accomplished by standard techniques such as recrystallization, chromatography, etc. Their purity and structure can be tested by conventional techniques such as thin film chromatography, high performance liquid chromatography, infrared spectroscopy, nuclear magnetic resonance and elemental analysis.

The sweetness of the composition thus prepared was evaluated by a group of 8 experienced testers. For this purpose, aqueous solutions of the compound at various concentrations are compared in sweetness with standard solutions of sucrose at concentrations corresponding to common uses, namely 2%, and in some cases 5% and 10%. It was done. Indeed, the sweetness of synthetic sweeteners varies as a function of the concentration of the sucrose solution used as a reference. Therefore, the sweetness of the compound tested compared to sucrose corresponds to the weight ratio existing between the compound and sucrose of the same sweetness intensity, i.e. the solution of the compound tested and the standard sucrose solution. sweetness tests were considered by a majority vote of the testers as having the same sweetness intensity.

The sweeteners of the present invention have the advantage that they can be added to beauty or cosmetic products in which sweetening is desired in proportions sufficient to provide the desired level of sweetness. The optimum application concentration of the sweetener depends on a variety of factors, such as the sweetness of the sweetener, storage conditions, type of food product, specific ingredients of the product, aromaticity of the beauty product, and desired level of sweetness. A person skilled in the art can easily determine the optimal ratio of sweeteners that must be used to obtain a beauty product by performing repeated taste analyses. Preferred sweeteners of the present invention are typically found in beauty products at about 0. It is added to beauty products in proportions from QO1 to about 1-02% by weight.

Obviously, concentrates contain a higher percentage of sweeteners,
It could then be diluted according to the extreme intended use.

A very important advantage of the sweeteners of the invention is that in many cases they do not have a licorice aftertaste, such as glycyrrhizin or thaumatin, but have a metallic or bitter taste, such as saccharin or acesulfame. without aftertaste,
It forms a sweet taste very similar to that of sucrose.

The heterocyclic or heterocyclic derivatives described in the present invention are based on the prior art (Lebensm, Unlers, Forsch,
1982, pp. 175, 266-268) and U.S. Patent Application Ser. As mentioned above, it has the advantage of having a solubility that is even more soluble in water than that successfully demonstrated in these documents under the same conditions.

Solubility was measured by the following method. The excess compound whose solubility is to be determined is diluted to pH 3 with phosphate buffer at temperature conditions around 0°C, corresponding to the preparation and storage temperature of carbonated beverages.
was added to the water dispersion prepared. This dispersion is
placed in an ice bath, then ultrasonically agitated for 60 minutes, and then 0.45 micron Millipore Millex-HV
Filter (Millipore Millex-■
V).

As a result, the saturated solution of the compound in the filtrate was determined by high performance liquid chromatography relative to a standard solution of known concentration.

In this method, for example, the compound described in the fourth example of the invention, in which component R is 2-cyanopyrid-5-yl, has an OoC of about 400111! /liter, but 2. Lcbe++sm, Unters
.

Forsch, the 4-cyanophenyl carbocyclic analog described in Example 16 has a solubility of only about 100 mg/lindole under the same conditions, thus the solubility of the heterocyclic derivative is lower than that of its carbocyclic analog. It was observed that it is about 4 times as large as that of . Similarly, for example, the compound described in the first embodiment of the invention, in which component R is a 5-benzofurazanyl group, has a solubility of about 1150 mg/liter at 0°C, and thus about 410 m(/'J Torr). The U.S. patent ratio fimg36.o7 with a solubility of about 2
It was observed that it was 8 times as large.

"Example" The invention will be explained below with reference to examples.

First Example Synthesis of 4-pyridylcarbamoyl-β-alanine A solution of 1 gram (10,64 mmol) of 4-aminopyridine and 2.3 grams (15,9 mmol) of β-alanine ethyl ester isocyanate was prepared at 30 rA
Q of anhydrous acetonitrile and stirred at room temperature for 20 hours. After concentrating to dryness and trituring the resulting oily residue in 50 ml of ether, 2.5 g (88% yield) of 4-pyridylcarbamoyl-β-alanine ethinoester was obtained with a melting point of 95°C. Obtained as a solid with

2 grams (8,4 mmol) of 4-pyridylcarbamoyl-β-alanine ethyl ester and 0.37 grams (9,2 mmol) of sodium hydroxide are
of methanol and 0.1 mM water at room temperature for 24 hours.
Stirred for an hour. After being concentrated to dryness, the resulting oily residue was transferred to 15 mA water. After washing three times with 10 ml of dichloromethane, the aqueous phase was acidified with 3N hydrochloric acid solution until a pH of 3 was obtained. The precipitate formed was filtered, washed with 1 OIIIA of cold water, and then dried. This resulted in 1.36 grams (95% yield) of 4-pyridylcarbamoyl-β-alanine as a solid with a melting point of 222°C.

The sugar content of this compound corresponded to about 50 times that of sucrose compared to a 2% sucrose solution on a weight basis.

Second Example Synthesis of 2-chloro-5-pyridylcarbamoyl-β-alanine 2 grams (i2°9 mmol) of β-2-chloro-5-pyridyl isosymol) dissolved in 25 mQ of benzene
- added to a 25 mA aqueous solution containing alanine and 0.75 grams (7 mmol) of sodium carbonate. This solution was stirred vigorously for 1 hour at room temperature, then 50 m
A was extracted three times with ethyl ether. The liquid phase was cooled and then acidified with 3N hydrochloric acid solution until a pH of approximately 3 was obtained. The generated precipitate was filtered and 10 m
11 of cold water and then dried. As a result,
1.5 grams (45% yield) of 2-chloro-5-pyridylcarbamoyl-β-alanine was obtained in solid form with a melting point of 200°C.

The sugar content of this compound corresponded to about 50 times that of sucrose compared to a 2% sucrose solution on a weight basis.

Third Example Synthesis of N-[2-chloro-5-aminopyridyl(imino)methyl]-2-aminoacetic acid A solution of 1.26 grams (14.2 milliliters.
2 grams (6,4 mmol) of 2-chloro-5-aminopyridylthiourea, 1 gram (7,68 mmol) of glycine tertiary butyl ester and 1.45 grams (7,0
A solution of dicyclohexylcarbodiimide (4 mmol) was added to 30 ml of ethyl acetate and heated at 60°C for 2.
Heated for 5 hours. The dicyclohexylthiourea precipitate formed was removed by filtration. The supernatant was concentrated to dryness and the resulting product was transferred to 20 mQ dichloromethane, followed by 0.25N dilute hydrochloric acid solution (4X 3
0ml). This acidic solution was then neutralized with IN sodium hydroxide followed by dichloromethane (
3x 20 ml), thus obtaining 0.65 g (36% yield) of tert-butyl-N-[2-lytetra-5-aminopyridyl(imino)methyl]-2-aminoacetic acid in oily form. It was done.

0.65 grams (2.3 mmol) of the ester thus produced were dissolved in 3.2 mQ (2.3 mmol) of a 7N hydrochloric acid solution in 1.5 mQ glacial acetic acid and dioxane. After 1.5 hours at room temperature, the solvent was removed under reduced pressure. The residue was transferred into ethyl ester (4 x 20 ml) and then dissolved in 15 mQ of saturated aqueous sodium carbonate. After washing three times with 10 mQ of dichloromethane, the liquid phase was brought to pH 4 with 3N hydrochloric acid solution. The precipitate formed was filtered, washed with 5 mQ of cold water and then dried. This resulted in a concentration of 0.1
1 gram (21% yield) of N-[2-chloro-5-aminopyridyl(imino)methyl]-2-aminoacetic acid
Obtained in solid form with a melting point of 40°C.

The sugar content of this compound corresponded to about 50 times that of sucrose compared to a 2% sucrose solution on a weight basis.

Fourth Example 2 - Synthesis of Cyano-5-pyridylcarbamoyl-β-alanine This compound was synthesized from β-alanine monohydrate and 2-cyano-5-alanine according to the experimental procedure described in Example 2. Obtained from pyridyl isocyanate (yield 24%, 1
melting point of 73°C).

This compound had a sugar content corresponding to approximately 700 times that of sucrose compared to a 2% sucrose solution on a weight basis.

Example 5 Synthesis of 2-cyano-5-pyrimidinylcarbamoyl)-β-alanine 0.83 grams (7 mmol) of 2-cyano-5-aminopyrimidine and 1 gram (7 mmol) of β-alanine ethyl ester isocyanate The solution was added to 30ml of anhydrous acetonitrile and heated at 70°C for 4 hours. The reaction mixture was concentrated to dryness and 0% 7 by 50 mC of hydrochloric acid in
It is directly hydrolyzed at 0°C for 3 hours, and after cooling, the pH
treated with sodium hydroxide until 10, 3×4
Washed with 0 mM dichloromethane, acidified with hydrochloric acid to pH 3, then concentrated to dryness in vacuo. This residue was purified by treatment with absolute ethanol of 100% purity and concentration of ethanol extraction to dryness to yield 0.74 grams (45% yield) of 2-cyano-5-pyrimidinylcarbamoyl)-β-alanine at 183°C.
It was obtained in the form of a solid with a melting point of .

The sugar content of this compound corresponded to about 400 times that of sucrose compared to a 2% sucrose solution on a weight basis.

Sixth Example 2-Cyano-5-pyrimidinylthiocarbamoyl-β-
Synthesis of Alanine This compound was obtained from β-alanine and 2-cyano-5-pyridinyl isothyenatrimonoxide (yield 13%, 135
melting point in °C).

This compound had a sugar content, on a weight basis, corresponding to approximately 1000 times that of sucrose compared to a 2% sucrose solution.

Seventh Example 5 - Synthesis of Benzofurazanyl Carbamoyl Glycine This compound was obtained from glycine and 5-benzofurazanyl isocyanate (68% yield, 212 melting point in °C).

The sugar content of this compound corresponded to about 20 times that of sucrose on a weight basis compared to a 2% sucrose solution.

Example 8 Synthesis of 5-Benzofurazanylcarbamoyl-β-alanine This compound was obtained from β-alanine and 5-benzofurazanyl isocyanate (47% yield) following the experimental procedure described in Example 2. , melting point of 208°C)
.

This compound had a sugar content, on a weight basis, corresponding to approximately 800 times that of sucrose compared to a 2% sucrose solution.

9th Example N-[5-benzo7lazanylamino(imino)methyl]
-Synthesis of 2-Amine Acetic Acid This compound was obtained from 5-benzofurazanylthiourea and glycine tertiary butyl ester (25% yield, 181 °C melting point).

The sugar content of this compound corresponded to about 200 times that of sucrose on a weight basis compared to a 2% sucrose solution.

Example 10 Synthesis of N-[cyanoimino(5-benzofurazanylamino)methyl]-3-aminopropionic acid 1.3 grams (
4,4 mmol) of 5-benzo7lazanylthiocarbamoyl ester, 0.371 grams (8.8 mmol) of cyanamide, 1.36 grams (6,6 mmol) of dicyclohexylcarbodiimide and 0.1 ml I A solution of triethylamine was left in 30 ml of anhydrous acetonitrile at room temperature for 40 hours. The mixture was concentrated to dryness so that the oily component was triturated in ethyl ester (3 x 30 ml) to give 1 gram (76% yield) of a solid. This solid is C H C
Ethyl-N-[cyanoimino(5benzofurazanylamino) with a melting point of 155 °C after being purified on a silica column with a flow ratio of 113/acetone of 90/10.
0.5 g of methyl]-3-aminopropionic acid was obtained.

0.5 g (1.65 mmol) of the ester and 0.066 g (1.65 mmol) of sodium hydroxide thus obtained were added to 15+1111 methanol and 0.1 mQ of water at room temperature. It was left for 30 hours. This mixture is concentrated to dryness and the resulting residue is lOrR1! of water was added and the residue was purified by washing with dichloromethane (3X20I+11).

As a result, the cooled liquid phase was acidified by adding 3N hydrochloric acid solution until pi() became 3.

The solid thus obtained was collected by filtration and then washed with 2×3 ml of water. After drying, 0.

2 grams (44% yield) of N-[cyanoimino(5benzofurazanylamino)methyl]-3-aminoflopionic acid (melting point 92°C) were obtained.

The sugar content of this compound corresponded to about 200 times that of sucrose on a weight basis compared to a 2% sucrose solution.

11th Example 1 - Oxide-5-benzofurazanylcarbamoyl-
Synthesis of β-Alanine This compound was obtained from β-alanine and 1-year-old oxide-5-benzo7 lazanyl isocyanate (76% yield, 1
melting point of 96°C).

This compound had a sugar content, on a weight basis, corresponding to approximately 500 times that of NEI Tong compared to a 2% sucrose solution.

Example 12 Synthesis of 5-Benzothiofurazanylcarbamoyl-β-alanine This compound was obtained from β-alanine and 5-benzothio7lazanyl isocyanate (harvested) according to the experimental procedure described in Example 2. 47%, melting point of 189°C).

The sugar content of this compound corresponded to about 50 times that of sucrose on a weight basis compared to a 2% sucrose solution.

Example 13 (IH-Indacyl-6-,Nyl)thiocarbamoyl-
Synthesis of β-alanine 5 grams (28,6 mmol) of IH-Indacylu6
- Niluinthiocyanate, 5.3 grams (34,3
A solution of β-alanine ethyl ester hydrochloride (1 mmol) and 4.8 mff1 (34.3 mmol) of triethylamine was left at room temperature for 1 hour with stirring in 50 mQ chloroform. The chloroform liquid phase is water (
2x 10mA) and IN hydrochloric acid solution (2x 10mn)
was washed with It was then concentrated to dryness. The remainder (8 grams) is the ethyl ester (3x20ml+)
3.1 grams (28% yield) of (IH-indazol-6-yl)thiocarbamoyl-β-alanine ethyl ester with a melting point of 145°C was obtained.

0.6 g (2.05 mmol) of ester and 0.09 g (2.36 mmol) of sodium hydroxide thus obtained were mixed with 15+++ Il of methanol and 0.1
ml of water and left with stirring at room temperature for 20 hours. After concentrating to dryness, the resulting residue contains 1
0ml of water was added. This residue is ethyl acetate (3X
After purification by extraction with 20mM), the resulting liquid phase is cooled and then diluted with 3N until the pH is 3.
acidified by a hydrochloric acid solution. Therefore, 0.293
(56% yield) of (LH-indasy-6-yl)thiocarbamoyl-β-alanine was obtained as a solid with a melting point of 175°C.

The sugar content of this compound corresponded to about 150 times that of sucrose on a weight basis compared to a 2% sucrose solution.

The sweetness levels of the various compositions shown in Examples 1-13 are summarized in Table 1 below. Sweetness is evaluated on a weight basis compared to a 2% sucrose solution.

No. ■ table R-NH-C-NH-(CH,).

OOH compound sweetness level

Claims (6)

[Claims] (1) It has the following general formula, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, the above R is a monocyclic or bicyclic heterocyclic group, and the above monocyclic group is the following: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, X is Cl, CN, or NO_2 group, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ However, if G_1 is CH or N Yes, G_2 is CH_2, CO, NH, NCH_3, O or S
, G_3 and G_4 are CH, CCH_3, N or NO, the A is O, S, NH or N-CN, NH is chlorinated in the form of hydrochloride, and the n is 1 or 2, wherein B is a sweetener having a heterocyclic group which is COOH or a sodium, potassium, ammonium, calcium or magnesium salt. (2) The above R is a 2-cyanopyrid-5-nyl group or a 2-cyanopyrid-5-yl group
-cyanopyrimidin-5-yl group, and the A is O or NH, and the n is 1 when A is NH, or 2 when A is O. Sweeteners listed in section. (3) Sweet foods, beverages, and candy to which an appropriate amount of at least one sweetener according to claim 1 is added;
Sweetening methods for pastries, chewing gum, hygiene products, cosmetics, toiletries, pharmaceutical and veterinary preparations, etc. (4) A sweetened preparation produced by the sweetening method according to claim 3. (5) an appropriate amount of the sweetener according to claim 1;
polydextrose, starch, maltodextrin,
Cellulose, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, microcrystalline cellulose, sodium alginate, pectin, gum, lactose, maltose, glucose, leucine, glycerol, mannitol, sorbitol, sodium bicarbonate, and phosphoric acid, citric acid, tartaric acid, fumaric acid, benzoic acid,
A sweetening composition comprising a carrier or filler selected from the group comprising sorbic acid and propionic acid and their sodium, potassium and calcium salts. (6) The sweetener according to claim 1, sucrose, corn syrup, fructose, aspartame, alitame, neohesparidin, dihydrochalcone,
Dehydrated isomaltose, stevioside, L-sugar, glycyrrhizin, kylitol, sorbitol, mannitol,
others selected from the group comprising acesulfame-K, saccharin and their sodium, potassium, ammonium or calcium salts, cyclamenic acid and its sodium, potassium, ammonium or calcium salts, trichlorogalactosacrose, monellin and thaumatin; A sweetener comprising a sweetener and a sweetener.